Unitary isomerization-alkylation system



.@UVHLLE Filed. Mayk 29 l mf f. i. i Y

UNI TARY I SObERI ZATION-LKYLTION SYSTEM NNQ.

Patented Feb.vv 1p1, 1947v UNITARY ISOMERIZATION-ALKYLATION SYSTEM .Edmond L. dOuv'ille, Chicago, Ill.,

Standard Oil Company, Chicago,

ati'on of Indiana assignor. to Ill., a corpo- Application May 29, 1943, Serial No. 488,964 l 2 Claims. l This invention'relates to a unitary isomerization-alkylation systemand it pertains more particularly to the isomerization of normal paraihns n such as normal butane and subsequent alkylation of the resulting isoparailnV with an olen such as ethylene by means of active metal halide catalysts for producing highly Vbranched-chain paralnic hydrocarbons such as diisopropyl which are valuable components of aviation fuel.

It is known that normal paralns Such as butane and pentane may be isomerized with catalysts of the active metal halide type, and it is known that the resulting isoparains may be alkylated with olens with similar catalysts or catalysts such as sulfuric acid and many systems have heretofore been proposed for combining such processes. The object of my invention is to provide an improvement in systems of this general type which offers important commercial advantages overV any such combination heretofore known to the art.

Aluminum chloride is quite soluble in light hydrocarbons such as butane and pentane particularly at temperatures upward of about 200 F. When such hydrocarbons are vi'somerized with catalysts consisting of or containing aluminum chloride at such temperatures there is therefore a marked tendency for the etlluent product to contain dissolved aluminum chloride and for this dissolved aluminum chloride to be carried over with the reaction eluent stream to other parts of the system wherein it may cause considerable corrosion and operating di'iculties and lead to high catalyst losses and large requirements of treating and neutralizing agents. In order to solve this aluminum chloride carry-over problem the art has resorted to many complicated and expensive expedients none of which is particularly desirable. When the isomerization is' effected at high temperature with highly active catalyst this carry-over problem becomes even more pronounced and those skilled in the art have therefore used lower temperatures, less active catalysts, clay absorbers, materials which precipitate the catalyst by chemical combination therewith, antisolvents, etc. in an eiort to minimize this carryover problem. An object of my invention is to provide' a system in which the catalyst. carry-over isnot a detriment but a positive benefit and .in which the isomerization may be effected at higher temperatures and with more active catalysts than have heretofore been commercially feasible whereby the isomerization reactor may be substantially reduced in size and the conversion per pass may be substantially increased.

The alkylation of isoparamns with olefns by means of 4halide catalysts is taught by U. S. Patents 2,308,560-1-2. An object of my invention the alkylation step,

is to improve the alkylation processes of these patents and to integrate such processes with isomerization in such a manner that both steps may be operated with increased efficiency andthe overall results may be remarkably and unexpectedly improved.

When aluminum chloride and hydrogen chlolride are the make-up catalyst materials employed in the isomerization and alkylation steps, optimum isomerization is effected with relatively high hydrogen chloride concentrations, i. e., concentrations of the order of 3 to 10%, e. g. about 5 or 6% by weight based on charging stock. In the alkylation step the hydrogen chloride concentration should be much lower, i. e., should be below 4% or as low as 0.5% by weight -based on aluminum chloride in the complex present or only a small fraction of a percent based on the charging stock. In the isomerization process catalyst consumption is relativelyrsmall and lfrom 50 to` 100 gallons of isomerization product may be produced per pound of added aluminum chloride; in

however, the catalyst requirement is much higher and usually only about 15 or 20 gallons of alkylate is produced per pound of aluminum chloride.

In practicing my invention I employ a more active catalyst in the isomerization step than has heretofore been commercially feasible. The activity of such catalyst material may be measured by its heat of hydrolysis which in turn can be determined by any well known calorimetric method wherein the temperature rise occasioned by the addition of one mol of complex to approximately 100 mols of Water can be measured. I have discovered 'that the optimum aluminum halide-hydrocarbon complex catalyst forv effecting isomerization are those which in the case of 1 aluminum chloride complexes have heats of hydrolysis between vthe approximate limits of 68 and large calories per gram atom of active aluminum, and in the case'of aluminum bromide complexes between 75 and 82 large calories per gram atom of active aluminum. By maintaining the activity of the isomerization catalyst within gleyse rather critical limits I obtain from 50 to 0 conversion with a smaller reactor than has heretofore been deemed necessary. Theexpression active alumin is used in this specication and in the accompanying claims refers to the aluminum content of the hydrolizable aluminum conversion per pass and I can Iobtain this i a 3 compounds in the aluminum halide-hydrocarbon complex; thus any aluminum in the form of oxide or hydroxide is not active aluminum since it is not hydrolzable.

To maintain the catalyst in the isomerization step at an activity oi 68vto 75 large calories per gram atom of active aluminum in the case of aluminum chloride it isnecessary that make-up aluminum chloride be added in larger quantities than are required for effecting the isomerization reaction and large amounts of this alumi-I num chloride are carried over in solution in the eiuent isomerization product stream. Instead of endeavoring to neutralize or remove this carryover aluminum chloride I utilize it in effecting a subsequent alkylation step. The entire eiiluent product stream however cannot be charged to the alkylation step because of its high hydrogen chloride content and in practicing my invention I reduce the pressure on the effluent product stream sufficient to release a substantial portion of the hydrogen chloride and to permit its separation and recycling back to the isomerization step. By controlling the pressure at which the hydrogen chloride is released I can retain the optimum amount of hydrogen chloride in the eiiiuent stream for use in the alkylation step. Any light hydrocarbon gases such as methane which might tend to accumulate in the system may be separated from-the recycled gas by absorbing the hydrogen chloride content thereof in a portion of the incoming charging stock and venting the unabsorbed gas. l y

A feature of my process is the maintenance of relatively high temperatures betweenthe isomerization and alkylation steps. The isomerization eiiiuent product stream may notonly contain dissolved aluminum chloride but may also contain other dissolved or mechanically entrained catalyst material the bulk of which can be separated from the stream by settling, centrifuging, filtration or other well known means. If cooling is employed for precipitating aluminum chloride the precipitate is in such a finely divided condition that it is extremely difficult .to separate. Adding to the complexity of the problem is the unusual type of supersaturation which is encountered. On cooling a saturated solution of aluminum chloride, precipitation is not rapid or complete even in a turbulent system and in the presence of solid aluminum chloride. Consequently systems provided with cool settlers encounter serious operating diiiiculties because of plugged lines down stream from said cool settlers. Extreme corrosion also has been observed down stream from cool settlers Where such precipitation takes place. By keeping the eiliuent prod. uct stream at high temperature enroute to the alkylationstep I may thus eliminate vor at least substantially minimize vexatious line plugging problems and corrosion diiiiculties.

It has heretofore been proposed to transfer catalyst complex from an isomerization reactor to an alkylation reactor but such practice offers the disadvantage of introducing into the alkylation zone any objectionable metal salts or other impurities which may accumulate in the isomerization zone. These impurities tend to increase the tendency toward cracking. Such tendency toward cracking is not a problem in the isomerization step because of the high, stability toward cracking exhibited by normal butane and by small amounts of cyclic However, the highly senthe pentanes containing cracking inhibitors. sitive hexanes and heptanes produced in 4 alkylation step might be deleteriously affected if such impurities were transferred from the isomerization step to the alkylation step. In my system impurities remain in the isomerizer andv it is only the desired' catalyst components which are' transferred from the isomerizer to the alkylation step.

In the alkylation step the make-up aluminum chloride may be supplied by the carry-over catalyst from the isomerization step and if any additional make-up catalyst is required it may be supplied by Icy-passing a part of a recycled isoparan stream through an aluminum chloride solution tank. The blending of the recycled isoparaiiin stream with the isomerization product stream gives a composition which not only contains exactly the right amount of aluminum chloride and hydrogen chloride but which is also at the right temperature for eiecting olefin alkylation. The olefin is preferably ethylene (which cannot successfully be alkylated by isoparailins in sulfuric acid systems) although other olelns may of course be used. The mol ratio of isoparaiiins to oleiins in the alkylation step should be at least 4:1 and preferably should be greater than 6:1. Y

Since the eiiiuent product stream leaving the alkylation step is substantially free from oleiins any light gases and hydrogen chloride separated therefrom may -be returned to the hydrogen chloride absorption step preceding the isomerization. The alkylate is then separated from the lower boiling paraiiins and the parafns are fractionated to give an isoparain recycle stream for the alkylation step and a normal paraffin recycle stream for the isomerization step.

An important feature of my invention is the use of cyclic hydrocarbon cracking inhibitors such as naphthenes in `both the isomerization and alkylation steps` Thus benzene, alkyl benzenes, cyclo pentane, methyl cyclopentanes, cyclohexanes, methyl cyclohexanes or the like may be added in small amounts to the charging stock entering the isomerization step and by using such inhibitors I may emplay even more severe reaction conditions and more highly active catalysts without causing an undue amount of cracking. In accordance with my invention such cracking inhibitors are carried with the eiliuent product stream from the isomerization step to the alkylation step and in the alkylation step to again serve as a cracking inhibitor and again to permit the use of more active catalysts and more severe operating conditions than would otherwise be possible.

The invention will be more clearly understood from the following detailed description read in conjunction with the accompanying drawing which forms a part of this speciiication and` which is a schematicow diagram of my improved isomerization-alkylation system.

Asa specific example of my invention I will describe the production of diisopropyl from butane and ethylene by means of an aluminuml chloride-hydrocarbonI complex promoted by hydrogen chloride. A substantially olen-iree butane stream is introduced from source I0 by pump II, about 50 to 80% of its being introduced by line I2 to the upper part of hydrogen chloride absorber I3 and the remaining 20 to 50% being introduced by pump llt-through heater I5 to aluminum chloride solution tank I6 and line I1 into reactor I8.

Absorber I3 may be operated at a pressure of approximately 300 pounds per square inch and at '800, for example, about 600 approximately atmospheric temperature so that hydrogen chloride from gases introduced by line I9 may be absorbed in the liquid butane'while -methane and other unabsorbed gases may be vented from the top oi the absorber through line 20. Make-up hydrogen chloride may be introduced through line 2| to line I9 or through line 2Ia to line 22 which leads from the bottom of absorber I3.. The hydrogen chloride solution is then introduced by pump 23 through heater 2t into the base of reactor I8, preferably through a suitable distributor 25. i

Reactor I8 is preferably a tower about 25 to 50 feet y"in height and before starting up. this reaction I introduce into the tower through-line 26 a preformed aluminum chloride hydrocarbon complex which may, for example, be prepared as described in U. S. Patent 2,300,249 although the introduced at I8a. The tower may be about onehalf to three-fourths full of this complex` material and I preferably employ a catalyst column in the complex which is .about to 30 feet or more in height. l

The reactor is operated under a pressure suilicient to maintain liquid phase conversion conditions, i. e., under a pressure of-about 400 to pounds per square inch. The tower is preferably koperated at 'ai approximately 300 pounds per lsquareiinc'h but temperature within 'the approximate .range of about 200 to 250 F. although lower temperatures may be employed with the consequent' lowering vof reaction rate and higher temperatures may be employed particularly when a cracking inhibitor is used as will hereinafter be described. In. this particular example, the tower is operated at a temperature of Aabout 212 F.

Make-up aluminum chloride is added to the column in butane solution through line I1, the solution tank is being repienished with iump aluminum. chloride from time to time through opening 2l. The amount of make-up aluminum chloride thus introduced may be readily controlled by controlling the temperature and amount of butane which is passed through soluy tion tank I6\,a sufcient time being allowed for' complete saturation in this solution tank. Fre- I' quently normal butane is not available 1in the high state of purity desired. Minute traces of olelns and sulfur impurities tend to coat over the-aluminum chloride'in solution tank -I6. In this situation aluminum chloride may be introduced to the isomerizer I8 by passing recycle butane from butane tower 59 by lines 63 and 63a to contact tower IB. This butane having been previously contacted with the catalyst has been freed from such impurities.

aluminum chloride in butane is approximately as follows:

` Pounds of e Weight por l Temperature cont of AlCla gglp'rr dissolved .butane .o1 .o2 .a .e 1.5 3.1 2.1 4.3' 250 F 5.5 11.3

. suiiicient to maintain such activity I The solubility of I add make-up aluminum chloride to tower I8 at a rateof about 1 to .4, e. g. about Z-pounds'per barrel of total butanes charged to reactor I8.

68 'and 75 large calories per'grainatom of active aluminum in the complex.

The space velocity in isomerization reactoris is preferably within the approidmategi-range of 0.4 to 4, e. g. about 1 volume of'butaneiperihour per volume of complex. Thei-upwardly ilowing butane stream is intimately dispersed inthe complex so that separate phases canhardly-be discerned but liquidreaction valve 29 to settler an which-maybe operated at slightly higher than the pressurefof absorber I3 and at an elevated temperaturepreferably about 200 to 250 F. Most oil-the.hydrogenjchloride together' with undissolved gases stiehlt'.y methane are taken overhead through line 'Bilandgreturned through line I9' to absorberl I3. 'AnyLentrained catalyst which settles out -in settler 30 is returned by line 32, pump 33 and line 26 to reactor I8. The remaining eilluent product stream which may contain about .1 to .4 pounds of dissolved aluminum chloride per barrel 'passes over Weir 33 and@ is withdrawn to alkylation reactor 35 through line 36 which ispreferably heavily insulated or even steam jacketed to prevent the precipitation of aluminum chloride. A recycleisobutane stream is introduced fromline 31 into reactor 35 at the point of discharge of line 36. For each volume of liquid introduced through line 3-6 I may introduce at least 4 or '5 volumes of recycled isobutane through line 37. Since the recycled isobutane may be at a temperatureA of about 80 l F'. and the temperature on stream in line 36 may be about 200 F., the temperature of the mixed stream envtering'reactor 35 may be at approximately 100 F. which is ideal fory eiecting the action. This entering stream will tain desired make-up aluminum chloride and hydrogen chloride for effecting the alkylation reaction. The activity of the catalyst in reactor 35 should bemaintained within the approximate range of 60 to 7 5 large calories per gram atom of active aluminum and if the` carry-over catalyst from the,product stream in line 36 is not may by-pass a part ofthe recycled isobutane stream through heater 38 and solution 'tank 39 for picking up any additional amount of make-.up Athat may be required; the lump aluminum chloride supply in solution tank 39 being replaced from time to time alkylation rethroughA opening 40. The solution is preferably 4:1 and preferably greater than v6:1. The alkypounds per-@barrel of vtotal products seeicairateout .from the upper surface of thepolurnn oig'com'plex and pass through line 28 and'fpreffssurefreducingg likewise conbe employed if cyclic cracking inhibitors are used.

The pressure should be sufficient to maintain liquid phase conditions and may be o i .the order of about 50 to 300, e. g. about 150 pounds per square inch. The space velocity may be approximY mately the same as in the isomerization step, i. e. about 0.4 to 4 volumes of liquid charge per hour per volume of complex in the reactor. With relatively high isoparafn to olefin ratios however the space velocities may be increased to as rnuch as 5 or 10 v./hr./v.

If it is desired to produce diisopropyl the catalyst activity should be in the general vicinity of about 65 to '10 large calories per gram atom of active aluminum. Usually this will mean that the complex contains roughly about 23 to 33% of bound hydrocarbons. Thus a catalyst activity of about 67 large calories per gram atom of alu- As another specific example of my invention I may employ a pentane charging stock to which has been added a small amount of a cracking inhibitor. It has been found that by adding about .02 to 3% or preferably.1 to 1% of an aromatic such as bentzol or about .2 to 20, preferably about 1 to 10% by volume f of a naphthne such as cyclopentane, methyl cyclopentane. cyclohexane, etc. cracking may be substantially inhibited and a relatively long catalyst life may be obtained. The inhibitor may be added to the charging stock through line or directly to the reactor through line 10a. In the case of aromatics, the inhibitor. should not .be chemically combined with the complex because aromatic complexes do not l inhibit cracking. Generally speaking, the conminum may produce chiefly diiscpropyl while a catalyst activityL of about 75 large calories per gram atom of active aluminum may produce a product in which the diisopropyl content is less` than the combined production of methyl pentane and neohexane.

The eiliuent product stream leaves the top of reactor 35 through line 43 to settler 44 from which any entrained complex may be settled out and returned to reactor 31 by lines `45 and 46. There may be a smallamount of complex formed in the isomerization system and any additional complex in this system transferred along with the efliuent product stream through line 316 to alkylation reactor 35. Likewise the bulk of complex in reactor 35 may tend to increase during the conversion. Any net production of complex may be continuoushz or intermittently withdrawn from the system through line ,41 for the recovery of valuable components or for other utilization.

Gases may -be .vented from the top of settler 44 through line 48 and such gases may if desired be compressed andreturned to line I9. The liquid alkylation product stream passes over weir 49 and is withdrawn through line 50to fractionator 5I whiohis provided with a suitable heater or reboiler 52 at its base. Alkylate is withdrawn from 1 the fractionator through line 53 and may 'be neutralized, water-washed and further fractionated for obtaining relatively pure diisopropyl or any other desired product fractions. The overhead from fractionator 5l (butanes and lighter) pass through cooler, 54 to receiver 55. A portion of the Aaccumulated liquid from receiver 55 is returned by pump 56 and line 51 to serve as refluxl in fractionator 5I. is introduced through line 59 to butane tower 59 which is likewise provided with a suitablere.-

boiler or heater 50 at its base. Normal butane is "withdrawn through line 6I and returned by hereinabove described. It will be understood that if the recycled stream is introduced in the abi sorber a suitable cooler will be employed.

The overhead isobutane stream from tower 59 passes through cooler 54 toreceiver 65. A part The remainder of this liquid l pump 62 and line 63 either to line I2 leading to absorber I3 or to solution tank I5 and line I1 as line 68 to line 31 for introduction into alkylation reactor 35. Any uncondensed gases may be vented from the top of accumulator 65 or introduced into line 98 or line I8.

version conditions in the case of pentane may be approximately the same as hereinabove described Weight f irimnis rr per cent o sso ve Temperature Alon in .uct per pentane bbl. pentane In the case oflpentane it has :'been noted that the amount of dissolved aluminum chloride is dependent upon whether or not the final solution temperature is approached from the low temperature side or the high temperature side of the solution temperature. The above table represents the solubilities when the solution temperature is approached from the low temperature side. When a mixtureV of pentane and aluminum chloride is heated to a higher temperature and then cooled tothe'desired solution temperature allowing as much as a half-hour for equilibrium to be reached it has been found that considerably more aluminum chloride can be dissolved as is indicated by the following table:

Weight f lounis (i per cent o isso ve Tempeml" mol, in Axel, per

pentane bbl. pentane (il 02 3 .7 2. 3 5. l il. l 6.8 7. l 15.6

num chloride it may be desiraible to effect the solution at a relatively high temperature and then cool the resulting solution to the extent necessary before introducing it through line I1 to reactor I8 or before returning it from solution tank 39 and line 4I to reactor 35.

When a cracking inhibitor is employed in the isomerization step this inhibitor is carried along with the effluent stream and introduced in'to the alkylation step wherein it likewise acts as an inhibitor and hence enables the use of higher temperatures or more severe operating conditions than would otherwise be feasible. When aromatics are employed there may be a certain amount 'of aromatic alkylation but the resulting alkylate panticularly in the case of pentanes when likewise functions as an inhibitor and may bea desired product. Naphthenes will have the advantage oi being unreactive in the alkylation step. The naphthenes or aromatics employed as inhibitors in the alkylation and isomerization steps may be selected so that they may be readily separated fromthe desired alkylation product (such as diisopropyl). Where the alkylation product is to be employed as an aviation motor fuel the inhibitor may be left in the product as a component of said fuel, particularly when said inhibitor is cyclopentane, methyl or polymethyl cyclopentane or a hydroaromatic' which is characterized by good antiknock properties particularly under rich mixture or supercharge conditions.

Advantageous results may also be obtained by g employing the cyclic hydrocarbon inhibitor in the butane isomerization and alkylation steps; the

stated critically small amount of aromatics and naphthenes may enable the use of temperatures of about 25 to 50 degrees higher than would otherwise be permissible so that any given installation would have a considerably increase throughput because of the increase in conversion effected by the more severe operating conditions made possible by the use offlnhibitor.

While I have describedfthe use oi' aluminum chloride and aluminum chloride-hydrocarbon complexes as my catalyst in the above examples it should be understood that the invention is not limited to such catalyst but is applicable generally to active metal halide catalysts. In the case of aluminum bromide the activity oi' the isomerization ,catalyst should be within the approximate range of 75 to 82 large calories per gram atom of active aluminum. My invention is also applicable to systems -wherein the isomerization ls eected by an active metal halide dissolved in an inert non-hydrocarbon liquid such as^ antimony trichloride because here again there is a pronounced tendency for the enluent product stream to carry over dissolved aluminum chloride and in accordance with my invention this carryover is not a detriment but is a positive beneilt.

While I havedescribed in .detail specific examples of my invention it should be understood that the invention is not limited to the particular system nor to any of the particular operating conditions set fbrth in these examples since numerous modifications andv alternative operating conditions will be apparent from the above description to those skilled in the v' Iclaim:

1. The method of synthesizing' hydrocarbons which method comprises 'isomerizing a normal paraffin hydrocarboirhaving at least four but less than six carbon atomsper molecule by contacting said parafiln hydrocarbon with an active metal halide isomerlzation catalyst and a substantial amount of a hydrogen halide activator in a first contacting zone under such conditions that substantial amounts of the active metal halide and hydrogen halide are carried away from the nrst contacting zone with isomerized hydrocarbons in the eiiluent product stream leaving 'said flrstcontacting zone, maintaining said eiiiuent product stream at'a high temperature which is not substantially lower than the temperature. maintained in said rst contacting zone while conveying said stream from said iirst contacting zone to a second contacting zone, removing mostl of the hydrogen halide from said stream bel fore said stream enters said second contacting zone, recycling said removed hydrogen halide to said rst contacting zone, introducing into said secondl contacting zone an olen hydrocarbon and a relatively large stream of recycled hydrocarbons hereinafter defined, passing ,the com-4 bined streams containing said olen hydrocarbon and isomerized parailn hydrocarbons through said second contacting zone in contact with an active metal halide alkylation catalyst under allqrlation conditions, employing an alkyla tion catalyst which requires make-up active metalhalirle in amounts at least equal to the amount of active metal halide dissolved in said eiiluent product stream, eifecting alkylation of said olefin with said isomerized parailln hydrocarbon by means of said alkylation catalyst which is thus fortified with active metal halide from the when combined therewith, and returningsaid cooled stream to said second contacting zone as said relatively large stream of recycled hydrocarbons. A

, 2. 'The method of claim 1 wherein the normal paraln hydrocarbon undergoing isomerization is normal'butane, wherein the olein is ethylene, wherein the `catalyst in the iirst contacting zone is an aluminum chloride-hydrocarbon complex having an activity in the range of about 68 to 75 large calories per gram atom of active aluminum and wherein the catalyst in the second contacting zone is an'aluminum chloride-hydrocarbon complex having an activity in the approximate range of 65 to 70 large calories per gram atom of active aluminum.

EDMOND L. D'OUVIILE. assumons crrnn The following references are of record in the :ille of this patent:

UNITED STATES PATENTS `Number Name l Date 2,316,775 Eglofi ..-'Apr. 20, 1943 2,308,561 Marschner et al. Jan. .19, i943 2,308,560 Carmody et al. Jan. 19, 1943 2,301,615 chenicek et a1 Nov. 1o, 1942 2,330,206 Dryer et al. Sept. 28, 1943 2,332,577 Kassel Oct. 26,v 1948 2,342,922 Danforth Feb. 29, 1944A :3,342,123

Danforth Fell. 22,1944 

